CN112941894A - Preparation method of microwave-induced graphene fiber non-woven fabric loaded with bismuth nanoparticles - Google Patents
Preparation method of microwave-induced graphene fiber non-woven fabric loaded with bismuth nanoparticles Download PDFInfo
- Publication number
- CN112941894A CN112941894A CN202110136784.0A CN202110136784A CN112941894A CN 112941894 A CN112941894 A CN 112941894A CN 202110136784 A CN202110136784 A CN 202110136784A CN 112941894 A CN112941894 A CN 112941894A
- Authority
- CN
- China
- Prior art keywords
- bismuth
- woven fabric
- graphene
- graphene oxide
- microwave
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Images
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/003—Treatment with radio-waves or microwaves
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4209—Inorganic fibres
- D04H1/4242—Carbon fibres
Abstract
The invention relates to a preparation method of microwave-induced graphene fiber non-woven fabric loaded bismuth nanoparticles. The method comprises the steps of weaving graphene into a non-woven fabric structure, and loading bismuth nanoparticles; and then microwave treatment is carried out on the bismuth particle-loaded graphene fiber non-woven fabric through microwaves to obtain fully-nanocrystallized bismuth nanoparticles, so that excellent electrochemical performance is obtained. The flexible graphene/bismuth nanoparticle non-woven fabric obtained by the invention has the advantages of excellent electrochemical performance and simple and convenient preparation method, is easy for industrial application, and simultaneously provides an effective way for quickly and conveniently synthesizing metal nanoparticles by the method for preparing bismuth nanoparticles by microwave induction.
Description
Technical Field
The invention belongs to the field of new material preparation, and particularly relates to a preparation method of microwave-induced graphene fiber non-woven fabric loaded bismuth nanoparticles.
Background
In recent years, with the development of integrated circuits, portable wearable electronic devices are widely used in our lives, and meanwhile, higher requirements are put on the endurance time of the portable wearable electronic devices. Unlike the rapid development of wearable electronic devices, the development of wearable energy storage devices is relatively slow. Therefore, how better wearable energy storage equipment of performance like frivolous, portable, the flexible characteristics of machinery such as ultracapacitor system, flexible battery have high energy density and power density concurrently simultaneously, and then better promotion flexible wearable electronic equipment's travelling comfort and portability realize the wearable integral type system of flexibility in the real sense, are the current problem that needs to solve urgently. Currently, lithium ion batteries remain the primary choice for energy storage devices due to their excellent performance. However, due to the scarcity of lithium resources in global distribution, the cost of the lithium resources is relatively high, and in contrast, the sodium resources are more abundant in reserves and low in cost, so that the sodium ion battery becomes an important development direction of future energy storage equipment. The portable flexible sodium ion energy storage device has wide application prospect due to the advantages of lightness, small size and the like, and the preparation of the flexible electrode material is the core of the flexible sodium ion energy storage device.
At present, sodium ion energy storage device (sodium ion hybrid capacitor, sodium ion battery etc.) has wide application prospect, but because sodium ion's ionic radius is bigger than lithium ion for sodium ion energy storage device has met some problems in the application, and great ionic radius makes sodium ion insert/take off the in-process that inserts and cause electrode material's volume change comparatively serious, leads to the material to smash even, causes irreversible capacity decay. In addition, the cathode material used for the sodium ion energy storage device has poor electrochemical reaction kinetics, so that the rate performance is poor, and the mechanical performance of the material prepared by the current flexible cathode material preparation method can not meet the requirement.
The reported preparation methods of some flexible sodium ion energy storage device cathode materials still have the problems of electrochemical reaction kinetic lag, poor reversibility, large irreversible capacity loss, poor mechanical stability and the like. The variety of selectable sodium ion negative electrode materials is wide, bismuth (Bi) is used as an alloy-based negative electrode material, and due to the unique layered crystal structure, the larger interlayer distance and the larger theoretical capacity, the bismuth (Bi) is widely researched in the sodium ion negative electrode materials in recent years. The bismuth nanoparticles and carbon composite material is prepared by a simple annealing method, and the bismuth nanoparticles are uniformly embedded in the carbon skeleton, so that the composite material has a uniform structure. The nanostructures may ensure fast kinetics while effectively relieving stress strain due to the volume change of bismuth. The composite material still has an ultra-long cycle life under a higher current density, and has excellent electrochemical performance; the Poplar and the like design a multi-core shell bismuth and nitrogen-doped carbon cathode material (Bi @ N-C), and a nano-scale bismuth ball is packaged by a conductive nitrogen-doped porous carbon shell, so that the huge volume change of bismuth in the charge and discharge process can be effectively prevented, and the rate capability and the long cycle capacity of the sodium ion battery are effectively improved. The large volume change (≈ 250%) of bismuth (Bi) in the charge-discharge alloying process becomes a primary problem in practical application thereof. In addition, the graphene non-woven fabric material has good flexibility and conductivity, is light and small in size, can be directly integrated on a wearable device through weaving, and has a good application prospect in flexible energy storage equipment.
Disclosure of Invention
The invention aims to solve the problems of poor mechanical stability, low capacity, hysteresis of electrochemical reaction kinetics and the like of the conventional flexible negative electrode material, and designs a preparation method of microwave-induced graphene fiber non-woven fabric loaded bismuth nanoparticles. According to the method, graphene with excellent physical properties is woven into a non-woven fabric structure, and meanwhile, bismuth nanoparticles are loaded, so that the excellent conductivity, flexibility and mechanical strength of the graphene are combined with the higher theoretical capacity of bismuth; and then microwave treatment is carried out on the bismuth particle-loaded graphene fiber non-woven fabric through microwaves to obtain fully-nanocrystallized bismuth nanoparticles, so that excellent electrochemical performance is obtained. The flexible graphene/bismuth nanoparticle non-woven fabric obtained by the invention has the advantages of excellent electrochemical performance and simple and convenient preparation method, is easy for industrial application, and simultaneously provides an effective way for quickly and conveniently synthesizing metal nanoparticles by the method for preparing bismuth nanoparticles by microwave induction.
The technical scheme of the invention is as follows:
a preparation method of microwave-induced graphene fiber non-woven fabric loaded with bismuth nanoparticles comprises the following steps:
(1) preparation of graphene oxide/N, N-dimethylformamide (GO/DMF):
placing the graphene oxide aqueous solution in a centrifugal tube, wherein the graphene oxide aqueous solution accounts for 1/6-1/3 of the volume of the centrifugal tube; adding 1/6-1/2N, N-dimethylformamide in the volume of the centrifuge tube, placing the centrifuge tube in a centrifuge at the rotation speed of 7000-11000rpm for 25-35min, reserving graphene oxide at the bottom after the centrifugation is finished, and removing supernatant; repeating the process of adding N, N-dimethylformamide, centrifuging and removing supernatant for 1-5 times to obtain 4-13mg/mL of DMF dispersion of graphene oxide;
wherein the concentration of the graphene oxide aqueous solution is 2-4 mg/mL;
(2) refining bismuth powder: putting bismuth powder into a mortar and grinding for 30-60 min to obtain bismuth particles with the particle size of 40-60 mu m;
(3) preparation of graphene oxide/bismuth/N, N-dimethylformamide:
adding bismuth powder into the graphene oxide/N, N-dimethylformamide (GO/DMF) obtained in the step (1), and magnetically stirring for 3-6h to obtain graphene oxide/bismuth/N, N-dimethylformamide;
wherein, 0.5-2mL of graphene oxide/N, N-dimethylformamide (GO/DMF) is added into each mg of bismuth powder;
(4) preparing a bismuth particle-loaded graphene oxide non-woven fabric material by wet spinning:
measuring the mixed solution obtained in the step (3) by using an injector, placing the injector on an injection machine, injecting the injector into the solidification solution at an injection speed of 3-18mL/h, weaving into a non-woven fabric structure, and after the injection is finished, placing the non-woven fabric at room temperature for drying;
(5) placing the dried non-woven fabric obtained in the step (4) in a drying dish, adding hydroiodic acid, heating to 60-120 ℃ in a sealed state, and keeping the temperature for 3-9 hours to obtain the graphene non-woven fabric loaded with bismuth microparticles;
wherein 0.1-0.3mL of hydroiodic acid is added per mg of nonwoven fabric on average.
(6) And (3) placing the non-woven fabric reduced in the step (5) in a high-temperature resistant container, filling rare gas into the container, placing the container in a microwave oven, and carrying out microwave heating for 1-20s under the power of 700-1200W to finally obtain the bismuth nanoparticle-loaded graphene non-woven fabric with the particle size distribution of 30-50 nm.
The coagulating liquid in the step (4) is ethyl acetate.
The high-temperature resistant container in the step (6) is a quartz bottle, and the rare gas is argon.
In the non-woven fabric structure, the diameter of the graphene fiber is 40-70 μm, and the distance between the graphene fibers is 30-80 μm.
The invention has the substantive characteristics that:
the invention obtains the target product through wet spinning, chemical thermal reduction and microwave treatment. Compared with other methods, the graphene non-woven fabric loaded with the bismuth nanoparticles has the following substantial characteristics. First, the reaction time is greatly shortened by the microwave treatment and instantaneous heating, and the method is simple, rapid and efficient, improves the heating efficiency compared with the traditional heating method, and has excellent nano-scale form control. Secondly, the good electrical conductivity of the graphene non-woven fabric contributes to local joule heating, and the good thermal conductivity as a carbon material contributes to the graphene non-woven fabric as a base material for instantaneous heating, which characteristics make it have a good ability to absorb microwave radiation. The high temperature of the instantaneous heating helps the metal bismuth with larger particle size to rapidly decompose into bismuth nanoparticles. Thirdly, the nano-scale metal bismuth particles can provide rapid reaction kinetics, improve electronic conductivity and ionic conductivity, and more importantly, can effectively relieve stress and strain caused by large volume change, so that excellent electrochemical performance is further obtained, and the circulation stability is ensured. Fourthly, the graphene non-woven fabric prepared by wet spinning is used as a matrix, so that the volume expansion of the bismuth nanoparticles can be effectively relieved, and meanwhile, due to the excellent conductivity of the graphene non-woven fabric, an electronic transmission channel connected with each other is also provided. Finally, due to the unique structure of the graphene, the graphene has high conductivity and mechanical strength and good electrochemical stability. The graphene is woven into a non-woven fabric structure, the traditional fabric does not have conductivity, so that the application of the traditional fabric in the field of wearable electronics is greatly limited, and the prepared electrode material has good flexibility by utilizing the excellent performance of the graphene, and has a good development prospect in a flexible sodium ion energy storage device.
The invention has the beneficial effects that:
the graphene non-woven fabric loaded with the bismuth nanoparticles and used for the sodium ion energy storage device is obtained through wet spinning, a chemical thermal reduction method and microwave treatment. The metal nanoparticles can be obtained more efficiently by the technical means of microwave instantaneous heating, the reaction time is short, and the ablation of the graphene-based main body can be effectively reduced. The particle size of bismuth is in a nanometer level, and the bismuth is uniformly distributed on the graphene non-woven fabric substrate, so that the electrochemical reaction kinetics is accelerated, the ionic conductivity and the electronic conductivity are improved, and better rate performance can be obtained. Meanwhile, by utilizing the excellent physical properties of the graphene, the obtained graphene non-woven fabric has better flexibility and mechanical strength. The flexible graphene fiber is combined with bismuth (Bi) with higher theoretical capacity, so that the flexible graphene fiber has higher mechanical property and better electrochemical property at the same time, and the method is not reported at present. Compared with the bismuth composite material in the literature, the graphene non-woven fabric loaded with the bismuth nanoparticles in the embodiment 4 of the invention still has a specific discharge capacity of 279mA h/g at a high current density of 5A/g. The bismuth nanoparticle-loaded graphene non-woven fabric prepared by the invention has excellent rate capability, cycle performance and mechanical stability, and can meet the use requirements of flexible sodium ion energy storage devices under various conditions.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of the product of example 4;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the nonwoven fabric of example 4;
FIG. 3 is a Scanning Electron Microscope (SEM) image of bismuth nanoparticles of the product of example 1;
FIG. 4 is a Scanning Electron Microscope (SEM) image of bismuth nanoparticles of the product of example 4;
FIG. 5 is a Scanning Electron Microscope (SEM) image of bismuth nanoparticles of the product of example 3;
FIG. 6 is a graph of rate capability data for the product of example 1;
FIG. 7 is a graph of rate capability data for the product of example 2;
FIG. 8 is a graph of rate capability data for the product of example 4;
Detailed Description
The present invention will be described in further detail below with reference to the accompanying drawings by way of preferred embodiments.
The invention designs a method for preparing a bismuth-loaded graphene non-woven fabric through wet spinning, and then obtaining a sodium ion energy storage device cathode material of the bismuth nanoparticle-loaded graphene fiber non-woven fabric through microwave-induced instantaneous heating, which comprises the following steps: (1) preparation of graphene oxide/N, N-dimethylformamide (GO/DMF): and putting the graphene oxide aqueous solution into a centrifugal tube, wherein the graphene oxide aqueous solution accounts for 1/6-1/3 of the volume of the centrifugal tube. And adding 1/6-1/2N, N-dimethylformamide in the volume of the centrifuge tube, placing the centrifuge tube into a centrifuge after the mass ratio of the centrifuge tubes is configured, rotating at 7000-11000rpm for 25-35min, reserving graphene oxide at the bottom after centrifugation is finished, and removing supernatant. Repeating the steps for 1-5 times (repeating means that repeating for 1-5 times from the beginning of adding the N, N-dimethylformamide with the volume of 1/6-1/2 centrifuge tube to the end of removing the supernatant), and finally obtaining the DMF dispersion liquid of the graphene oxide with the concentration of 4-13 mg/mL; (2) refining bismuth powder: putting bismuth powder into a mortar and grinding for 30-60 min to obtain bismuth particles with the particle size of 40-60 mu m; (3) preparation of graphene oxide/bismuth/N, N-dimethylformamide: weighing 10-150mg of bismuth powder, adding into the graphene oxide/N, N-dimethylformamide (GO/DMF) obtained in the step (1), and stirring for 3-6h by using a magnetic stirrer to finally obtain graphene oxide/bismuth/N, N-dimethylformamide; (4) preparing a bismuth microparticle-loaded graphene oxide non-woven fabric material by wet spinning: measuring the mixed solution obtained in the step (3) with a certain volume by using a 10mL medical injector, placing the injector on an injection machine, injecting the injector into ethyl acetate at an injection speed of 3-18mL/h, weaving into a non-woven fabric structure, and after the injection is finished, placing the non-woven fabric at room temperature for drying; (5) and (3) placing the dried non-woven fabric obtained in the step (4) in a drying dish, adding 2-6mL of hydroiodic acid, heating to 60-120 ℃ in an electric heating oven, and keeping the temperature for 3-9 h. And obtaining the graphene non-woven fabric loaded with the bismuth microparticles. (6) And (3) placing the non-woven fabric reduced in the step (5) in a quartz bottle, operating in a glove box to fill argon into the bottle, placing in a microwave oven, and carrying out microwave heating for 1-20s under the power of 700-1200W to finally obtain the bismuth nanoparticle-loaded graphene non-woven fabric.
For a better understanding of the present invention, the present invention will be described in detail with reference to the following examples, but it should be understood that these examples are only for illustrative purpose and not for limiting the present invention. The experimental raw materials used in the following examples are commercially available or can be prepared by conventional methods known to those skilled in the art; the laboratory instruments used are commercially available.
Example 1:
the method comprises the following steps: placing the graphene oxide aqueous solution with the concentration of 3mg/mL into a centrifugal tube, wherein the graphene oxide aqueous solution accounts for 1/3 of the volume of the centrifugal tube. And adding 1/5N, N-dimethylformamide with the volume of the centrifuge tube, placing the centrifuge tubes into a centrifuge after the mass ratio of the centrifuge tubes is prepared, rotating at 9000rpm for 25min, reserving graphene oxide at the bottom after the centrifugation is finished, and removing supernatant. Repeating the steps for 2 times to finally obtain a DMF dispersion liquid of 6mg/mL graphene oxide;
step two: putting the original bismuth powder into a mortar for grinding for 40min to obtain bismuth particles with the particle size of 40-60 mu m;
step three: weighing 10mg of bismuth powder, adding the bismuth powder into 5mL of graphene oxide/N, N-dimethylformamide (GO/DMF) obtained in the first step, and stirring for 3 hours by using a magnetic stirrer to finally obtain a graphene oxide/bismuth/N, N-dimethylformamide mixed solution;
step four: measuring 4mL of the mixed solution obtained in the previous step by using a 10mL medical injector, placing the injector on an injection machine, completely injecting the injector into ethyl acetate at the injection speed of 12mL/h, weaving into a non-woven fabric structure, and after the injection is finished, placing the non-woven fabric at room temperature for drying; the mass of each piece of non-woven fabric obtained in the experiment is 20-35 mg; in the non-woven fabric structure, the diameter of the graphene fiber is 40-70 μm, and the distance between the graphene fibers is 30-80 μm;
step five: placing the single piece of dried non-woven fabric (25mg) obtained in the fourth step in a drying dish, adding 5mL of hydroiodic acid, sealing and heating to 120 ℃ in an electric heating oven, and keeping the temperature for 3 hours. And obtaining the graphene non-woven fabric loaded with the bismuth microparticles.
Step six: and (3) placing the non-woven fabric subjected to reduction in the previous step into a quartz bottle, operating in a glove box, filling argon into the bottle, placing the bottle into a microwave oven, and performing microwave heating for 7s under the power of 700W to finally obtain the bismuth nanoparticle-loaded graphene non-woven fabric.
Example 2:
the other steps of the preparation method of this example are the same as those of example 1, and the main difference is the microwave time. Finally obtaining the bismuth nanoparticle-loaded graphene non-woven fabric sodium ion energy storage material with different particle size distributions;
the method comprises the following steps: placing the graphene oxide aqueous solution with the concentration of 3mg/mL into a centrifugal tube, wherein the graphene oxide aqueous solution accounts for 1/3 of the volume of the centrifugal tube. And adding 1/5N, N-dimethylformamide with the volume of the centrifuge tube, placing the centrifuge tubes into a centrifuge after the mass ratio of the centrifuge tubes is prepared, rotating at 9000rpm for 25min, reserving graphene oxide at the bottom after the centrifugation is finished, and removing supernatant. Repeating the steps for 2 times to finally obtain a DMF dispersion liquid of 6mg/mL graphene oxide;
step two: putting the original bismuth powder into a mortar for grinding for 40min to obtain bismuth particles with the particle size of 40-60 mu m;
step three: weighing 10mg of bismuth powder, adding the bismuth powder into 5mL of graphene oxide/N, N-dimethylformamide (GO/DMF) obtained in the first step, and stirring for 3 hours by using a magnetic stirrer to finally obtain a graphene oxide/bismuth/N, N-dimethylformamide mixed solution;
step four: measuring 4mL of the mixed solution obtained in the previous step by using a 10mL medical injector, placing the injector on an injection machine, completely injecting the injector into ethyl acetate at the injection speed of 12mL/h, weaving into a non-woven fabric structure, and after the injection is finished, placing the non-woven fabric at room temperature for drying; the mass of each piece of non-woven fabric obtained in the experiment is 20-35 mg; in the non-woven fabric structure, the diameter of the graphene fiber is 40-70 μm, and the distance between the graphene fibers is 30-80 μm;
step five: placing the single piece of dried non-woven fabric (25mg) obtained in the fourth step in a drying dish, adding 5mL of hydroiodic acid, sealing and heating to 120 ℃ in an electric heating oven, and keeping the temperature for 3 hours. And obtaining the graphene non-woven fabric loaded with the bismuth microparticles.
Step six: and (3) placing the non-woven fabric subjected to reduction in the previous step into a quartz bottle, operating in a glove box, filling argon into the bottle, placing the bottle into a microwave oven, and performing microwave heating for 9s under the power of 700W to finally obtain the bismuth nanoparticle-loaded graphene non-woven fabric.
Example 3:
the method comprises the following steps: placing the graphene oxide aqueous solution with the concentration of 3mg/mL into a centrifugal tube, wherein the graphene oxide aqueous solution accounts for 1/3 of the volume of the centrifugal tube. And adding 1/5N, N-dimethylformamide with the volume of the centrifuge tube, placing the centrifuge tubes into a centrifuge after the mass ratio of the centrifuge tubes is prepared, rotating at 9000rpm for 25min, reserving graphene oxide at the bottom after the centrifugation is finished, and removing supernatant. Repeating the steps for 2 times to finally obtain a DMF dispersion liquid of 6mg/mL graphene oxide;
step two: putting the original bismuth powder into a mortar for grinding for 40min to obtain bismuth particles with the particle size of 40-60 mu m;
step three: weighing 10mg of bismuth powder, adding the bismuth powder into 5mL of graphene oxide/N, N-dimethylformamide (GO/DMF) obtained in the first step, and stirring for 3 hours by using a magnetic stirrer to finally obtain a graphene oxide/bismuth/N, N-dimethylformamide mixed solution;
step four: measuring 4mL of the mixed solution obtained in the previous step by using a 10mL medical injector, placing the injector on an injection machine, completely injecting the injector into ethyl acetate at the injection speed of 12mL/h, weaving into a non-woven fabric structure, and after the injection is finished, placing the non-woven fabric at room temperature for drying; the mass of each piece of non-woven fabric obtained in the experiment is 20-35 mg; in the non-woven fabric structure, the diameter of the graphene fiber is 40-70 μm, and the distance between the graphene fibers is 30-80 μm;
step five: placing the single piece of dried non-woven fabric (25mg) obtained in the fourth step in a drying dish, adding 5mL of hydroiodic acid, sealing and heating to 120 ℃ in an electric heating oven, and keeping the temperature for 3 hours. And obtaining the graphene non-woven fabric loaded with the bismuth microparticles.
Step six: and (3) placing the non-woven fabric subjected to reduction in the previous step into a quartz bottle, operating in a glove box, filling argon into the bottle, placing the bottle into a microwave oven, and performing microwave heating for 12s under the power of 700W to finally obtain the bismuth nanoparticle-loaded graphene non-woven fabric.
Example 4:
the other steps of the preparation method of the embodiment are the same as those of embodiment 2, and the main difference is that a mixed solution with a larger volume is measured for spinning, and finally the thicker graphene non-woven fabric sodium ion energy storage material loaded with the bismuth nanoparticles is obtained in the same area;
the method comprises the following steps: placing the graphene oxide aqueous solution with the concentration of 3mg/mL into a centrifugal tube, wherein the graphene oxide aqueous solution accounts for 1/3 of the volume of the centrifugal tube. And adding 1/5N, N-dimethylformamide with the volume of the centrifuge tube, placing the centrifuge tubes into a centrifuge after the mass ratio of the centrifuge tubes is prepared, rotating at 9000rpm for 25min, reserving graphene oxide at the bottom after the centrifugation is finished, and removing supernatant. Repeating the steps for 2 times to finally obtain a DMF dispersion liquid of 6mg/mL graphene oxide;
step two: putting the original bismuth powder into a mortar for grinding for 40min to obtain bismuth particles with the particle size of 40-60 mu m;
step three: weighing 10mg of bismuth powder, adding the bismuth powder into 5mL of graphene oxide/N, N-dimethylformamide (GO/DMF) obtained in the first step, and stirring for 3 hours by using a magnetic stirrer to finally obtain a graphene oxide/bismuth/N, N-dimethylformamide mixed solution;
step four: measuring 5mL of the mixed solution obtained in the previous step by using a 10mL medical injector, placing the injector on an injection machine, completely injecting the injector into ethyl acetate at the injection speed of 12mL/h, weaving into a non-woven fabric structure, and after the injection is finished, placing the non-woven fabric at room temperature for drying; the mass of each piece of non-woven fabric obtained in the experiment is 20-35 mg; in the non-woven fabric structure, the diameter of the graphene fiber is 40-70 μm, and the distance between the graphene fibers is 30-80 μm;
step five: placing the single piece of dried non-woven fabric (33mg) obtained in the fourth step in a drying dish, adding 5mL of hydroiodic acid, sealing and heating to 120 ℃ in an electric heating oven, and keeping the temperature for 3 hours. And obtaining the graphene non-woven fabric loaded with the bismuth microparticles.
Step six: and (3) placing the non-woven fabric subjected to reduction in the previous step into a quartz bottle, operating in a glove box, filling argon into the bottle, placing the bottle into a microwave oven, and performing microwave heating for 9s under the power of 700W to finally obtain the bismuth nanoparticle-loaded graphene non-woven fabric.
Fig. 1 is an X-ray diffraction pattern of a bismuth nanoparticle-loaded graphene non-woven fabric, a characteristic diffraction peak of a bismuth nanoparticle-loaded graphene non-woven fabric sodium ion energy storage material prepared by microwave-induced instantaneous heating of the invention is completely matched with a characteristic peak of pure bismuth, fig. 2 is a scanning electron microscope photograph of an overall structure of the graphene non-woven fabric, fig. 3 and 4 are scanning electron microscope photographs of the bismuth nanoparticle-loaded graphene non-woven fabric after microwave heating for 7s, 9s and 12s, and it can be seen from the scanning electron microscope photograph that after microwave heating for 9s, bismuth particles with a particle size distribution of 40-60 μm are rapidly decomposed into bismuth nanoparticles with a particle size distribution of 30-50 nm. The nano-scale metal bismuth particles can provide rapid reaction kinetics, and effectively relieve stress and strain caused by large volume change, so that excellent electrochemical performance is further obtained, and the cycling stability is ensured. The graphene serving as a matrix has excellent physical properties and also greatly contributes to the electrochemical properties of the whole material. Fig. 6 and 7 show multiplying power performance data of the bismuth nanoparticle-loaded graphene non-woven fabric energy storage material, the usage amount of the mixed solution is 4mL, the prepared non-woven fabric has higher specific discharge capacities of 333mA h/g and 384mA h/g at a current density of 1A/g after microwave time of 7s and 9s, fig. 8 shows multiplying power performance data of the bismuth nanoparticle-loaded graphene non-woven fabric energy storage material, the usage amount of the mixed solution is 5mL, and the specific discharge capacity of the prepared non-woven fabric can reach 279mA h/g at a higher current density of 5A/g after microwave time of 9s, so that the bismuth nanoparticle-loaded graphene non-woven fabric energy storage material has excellent performance.
Electrochemical performance tests were performed on the batteries of the examples (using the nover cell test system, the voltage range was selected to be 0.01 to 2V, and the current density was 0.1 to 5A/g, and the results are shown in table 1.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
TABLE 1 test results of specific discharge capacity and capacity retention rate of batteries of each example
The table above shows the rate performance data of the bismuth nanoparticle-loaded graphene non-woven fabric energy storage material, the nano-sized metal bismuth particles can provide rapid reaction kinetics, and the flexible graphene fibers are combined with bismuth (Bi) with higher theoretical capacity to simultaneously obtain good mechanical properties and excellent electrochemical properties, in example 4, after 9s of microwave time, the prepared non-woven fabric can obtain a higher specific discharge capacity of 393mA h/g at a current density of 1A/g, and even at a higher current density of 5A/g, the specific discharge capacity can still reach 279mA h/g. Meanwhile, the graphene non-woven fabric is used as a substrate, so that the volume expansion of the bismuth nanoparticles can be effectively relieved, and the capacity retention rate is still over 80% after 2000 cycles, wherein in example 4, the capacity retention rate is higher than 91%.
The invention is not the best known technology.
Claims (5)
1. A preparation method of microwave-induced graphene fiber non-woven fabric loaded with bismuth nanoparticles is characterized by comprising the following steps:
(1) preparation of graphene oxide/N, N-dimethylformamide (GO/DMF):
placing the graphene oxide aqueous solution in a centrifugal tube, wherein the graphene oxide aqueous solution accounts for 1/6-1/3 of the volume of the centrifugal tube; adding N, N-dimethylformamide with the volume of 1/6-1/2 centrifuge tube, placing the mixture into a centrifuge for centrifuging for 25-35min, reserving graphene oxide at the bottom after centrifuging is finished, and removing supernatant; repeating the process of adding N, N-dimethylformamide, centrifuging and removing supernatant for 1-5 times to obtain 4-13mg/mL of DMF dispersion of graphene oxide;
wherein the concentration of the graphene oxide aqueous solution is 2-4 mg/mL;
(2) refining bismuth powder: putting bismuth powder into a mortar and grinding for 30-60 min to obtain bismuth particles with the particle size of 40-60 mu m;
(3) preparation of graphene oxide/bismuth/N, N-dimethylformamide:
adding bismuth powder into the graphene oxide/N, N-dimethylformamide (GO/DMF) obtained in the step (1), and magnetically stirring for 3-6h to obtain graphene oxide/bismuth/N, N-dimethylformamide;
wherein, 0.5-2mL of graphene oxide/N, N-dimethylformamide (GO/DMF) is added into each mg of bismuth powder;
(4) preparing a bismuth particle-loaded graphene oxide non-woven fabric material by wet spinning:
measuring the mixed solution obtained in the step (3) by using an injector, placing the injector on an injection machine, injecting the injector into the solidification solution at an injection speed of 3-18mL/h, weaving into a non-woven fabric structure, and after the injection is finished, placing the non-woven fabric at room temperature for drying;
(5) placing the dried non-woven fabric obtained in the step (4) in a drying dish, adding hydroiodic acid, heating to 60-120 ℃ in a sealed state, and keeping the temperature for 3-9 hours to obtain the graphene non-woven fabric loaded with bismuth microparticles;
wherein 0.1-0.3mL of hydroiodic acid is added into each milligram of non-woven fabric on average;
(6) and (3) placing the non-woven fabric reduced in the step (5) in a high-temperature resistant container, filling rare gas into the container, placing the container in a microwave oven, and carrying out microwave heating for 1-20s under the power of 700-1200W to finally obtain the bismuth nanoparticle-loaded graphene non-woven fabric with the particle size distribution of 30-50 nm.
2. The method for preparing the microwave-induced graphene fiber non-woven fabric loaded with bismuth nanoparticles as claimed in claim 1, wherein the solidifying liquid in the step (4) is ethyl acetate.
3. The method for preparing the microwave-induced graphene fiber non-woven fabric loaded bismuth nanoparticles as claimed in claim 1, wherein the high-temperature resistant container in the step (6) is a quartz bottle, and the rare gas is argon.
4. The method for preparing the microwave-induced graphene fiber non-woven fabric loaded with the bismuth nanoparticles as claimed in claim 1, wherein in the non-woven fabric structure, the diameter of the graphene fibers is 40-70 μm, and the spacing between the graphene fibers is 30-80 μm.
5. The method for preparing the microwave-induced graphene fiber non-woven fabric loaded with bismuth nanoparticles as claimed in claim 1, wherein the rotation speed of the centrifuge in the step (1) is 7000-11000 rpm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110136784.0A CN112941894A (en) | 2021-02-01 | 2021-02-01 | Preparation method of microwave-induced graphene fiber non-woven fabric loaded with bismuth nanoparticles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110136784.0A CN112941894A (en) | 2021-02-01 | 2021-02-01 | Preparation method of microwave-induced graphene fiber non-woven fabric loaded with bismuth nanoparticles |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112941894A true CN112941894A (en) | 2021-06-11 |
Family
ID=76240791
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110136784.0A Withdrawn CN112941894A (en) | 2021-02-01 | 2021-02-01 | Preparation method of microwave-induced graphene fiber non-woven fabric loaded with bismuth nanoparticles |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112941894A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114823153A (en) * | 2022-04-24 | 2022-07-29 | 华星先进科学技术应用研究(天津)有限公司 | Flexible sodium ion capacitor electrode material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106410128A (en) * | 2016-07-18 | 2017-02-15 | 苏州大学 | Preparation method of graphene-bismuth oxide composite material for lithium ion battery negative electrode |
| CN107502995A (en) * | 2017-08-08 | 2017-12-22 | 杭州高烯科技有限公司 | Graphene fiber and graphene fiber non-woven fabrics of a kind of fold and preparation method thereof |
| CN108735983A (en) * | 2018-04-04 | 2018-11-02 | 广东工业大学 | A kind of metal nanoparticle is carried on graphene hydrogel composite material and its preparation method and application |
| CN109888190A (en) * | 2019-04-19 | 2019-06-14 | 河北工业大学 | A kind of sodium ion energy storage graphene/sodium titanate nonwoven cloth material preparation method |
-
2021
- 2021-02-01 CN CN202110136784.0A patent/CN112941894A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106410128A (en) * | 2016-07-18 | 2017-02-15 | 苏州大学 | Preparation method of graphene-bismuth oxide composite material for lithium ion battery negative electrode |
| CN107502995A (en) * | 2017-08-08 | 2017-12-22 | 杭州高烯科技有限公司 | Graphene fiber and graphene fiber non-woven fabrics of a kind of fold and preparation method thereof |
| CN108735983A (en) * | 2018-04-04 | 2018-11-02 | 广东工业大学 | A kind of metal nanoparticle is carried on graphene hydrogel composite material and its preparation method and application |
| CN109888190A (en) * | 2019-04-19 | 2019-06-14 | 河北工业大学 | A kind of sodium ion energy storage graphene/sodium titanate nonwoven cloth material preparation method |
Non-Patent Citations (2)
| Title |
|---|
| O. V. KHARISSOVA 等: "THE MICROWAVE HEATING TECHNIQUE FOR OBTAINING BISMUTH NANOPARTICLES", 《PHYSICS, CHEMISTRY AND APPLICATION OF NANOSTRUCTURES：REVIEWS AND SHORT NOTES》 * |
| 金玉强: "铋纳米材料作为锂/钠离子电池负极材料的制备与性能研究", 《中国优秀博硕士学位论文全文数据库（硕士） 工程材料Ⅱ缉》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114823153A (en) * | 2022-04-24 | 2022-07-29 | 华星先进科学技术应用研究(天津)有限公司 | Flexible sodium ion capacitor electrode material |
| CN114823153B (en) * | 2022-04-24 | 2023-11-03 | 华星先进科学技术应用研究(天津)有限公司 | Flexible sodium ion capacitor electrode material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | MnO@ 1-D carbon composites from the precursor C 4 H 4 MnO 6 and their high-performance in lithium batteries | |
| CN106784819B (en) | A kind of lithium sulfur battery anode material and preparation method thereof | |
| CN109449404A (en) | A kind of lithium sulfur battery anode material sulphur-nitrogen-doped carbon nano-fiber-MXene composite material and preparation method | |
| CN109273680A (en) | A kind of porous silicon-carbon cathode material and preparation method thereof and lithium ion battery | |
| CN105977458A (en) | Nano diamond powder and graphene composite electrode material and preparation method thereof | |
| CN107248569B (en) | Antimony/nitrogen-doped carbon composite prepared by taking 1-ethyl-3-methylimidazol dicyandiamide as carbon source and preparation method and application thereof | |
| CN105958033B (en) | A kind of preparation method and application of non-graphitized carbon nanotube/sulphur composite material | |
| CN111129475A (en) | Preparation method of molybdenum dioxide/carbon/silicon dioxide nanospheres and negative electrode material of lithium ion battery | |
| CN109411713A (en) | The machinery of the modified composite material of siliceous substrates material is total to method for coating, modified composite material and lithium ion battery | |
| CN108539147A (en) | A kind of preparation method and application of lithium ion battery negative material SiO@Al@C | |
| CN107170974A (en) | A kind of carbon coating MoSe2/ graphene electro spinning nano fiber and preparation method thereof | |
| Zhao et al. | Facile preparation of micron-sized silicon-graphite‑carbon composite as anode material for high-performance lithium-ion batteries | |
| Xu et al. | Encapsulating iron oxide@ carbon in carbon nanofibers as stable electric conductive network for lithium-ion batteries | |
| Chen et al. | Ultrafine MoO 2 nanoparticles encapsulated in a hierarchically porous carbon nanofiber film as a high-performance binder-free anode in lithium ion batteries | |
| CN112941894A (en) | Preparation method of microwave-induced graphene fiber non-woven fabric loaded with bismuth nanoparticles | |
| Yao et al. | Mace-like carbon fibers@ Fe3O4@ carbon composites as anode materials for lithium-ion batteries | |
| Liang et al. | Fast Energy Storage of SnS2 Anode Nanoconfined in Hollow Porous Carbon Nanofibers for Lithium‐Ion Batteries | |
| CN105702938A (en) | Iron-based oxide lithium ion battery negative electrode material and preparation method and application thereof | |
| Luo et al. | Porous Ti2 Nb 1 0 O 2 9− x Microspheres Wrapped by Holey-Reduced Graphene Oxide as Superior Anode Material for High-rate Performance Lithium-ion Storage | |
| CN112786869A (en) | Preparation method of ferric oxide/spiral carbon nanofiber composite anode material | |
| Wang et al. | Optimal quantity of nano-silicon for electrospun silicon/carbon fibers as high capacity anodes | |
| Wu et al. | Mixed-solvothermal synthesis and morphology-dependent electrochemical properties of α-Fe 2 O 3 nanoparticles for lithium-ion batteries | |
| CN105990566B (en) | Nickel oxide composite negative pole material and preparation method thereof | |
| CN107195897B (en) | Nano FeNbO4Graphene composite material and preparation and application thereof | |
| CN115498151A (en) | Preparation method of niobium pentoxide/graphene lithium ion negative electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20210611 |